Cleaning and whitening softener compositions

ABSTRACT

CLEANING AND WHITENING SOFTENER FORMULATIONS CONTAINING FROM ABOUT 4 TO 50% QUATERNARY AMMONIUM SOFTENER, 25 TO 94% OF CERTAIN POLYPHOSPHONIC ACID SALTS, 0 TO 31% OF AN ALKALI METAL POLYACETATE SEQUESTERING AGENT AND 0.01 TO 4% OF AN OPTICAL BRIGHTENER.

United States Patent CLEANING AND WEHTENING SOFTENER COMPOSITIONS Charles Bruce McCarty, Cincinnati, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio No Drawing. Filed Dec. 29, 1967, Ser. No. 694,368 Int. Cl. 344d 5/06; D061n 13/46 US. Cl. 117-335 7 Claims ABSTRACT OF THE DISCLOSURE Cleaning and whitening softener formulations containing from about 4 to 50% quaternary ammonium softener, 25 to 94% of certain polyphosphonic acid salts, 0 to 31% of an alkali metal polyacetate sequeste ing agent and 0.01 to 4% of an optical brightener.

This invention relates to compositions useful in the treatment of textile materials and to a method of imparting improved cleaning, brightening and softening properties to laundered textiles. More particularly, it relates to powdered or granular softener compositions having improved overall cleaning and whitening properties and useful for the softening of textile fabrics in a repetitious but generally discontinuous cycle which involves soiling, laundering, rinsing, soiling, etc.

BACKGROUND OF THE INVENTION The use of synthetic detergent composition in heavyduty household laundering has become a widespread practice. The formulations conventionally employed generally comprise synthetic detergent surfactants and certain alkaline so-called builder materials which function to enhance the cleaning levels of synthetic materials. Some inorganic builder materials present in detergent formulations have been known to have a tendency to react with the metal ions present in the washing solution precipitating out insoluble salts which deposit on the textile material being laundered. Such deposited mineral salts weaken the laundered fabrics, particularly at those areas of the fabric which are exposed to frictional and creasing effects such as collars and cuffs. This weakening of laundered fabrics and resulting loss of useful life which is encountered in the course of frequent laundering have in part resulted in the creation of a' large and expanding market for softener formulations capable of improving the softness or hand of laundered textiles. It has been found that the teratment of such materials with softening agents improves their softness of feel and prolongs the useful life of the textile materials. In addition, it has been found that such treatment generally results in a fabric having a reduced tendency to accumulate electrical charges which fact facilitates the ironing of treated materials.

The compositions commonly employed in home laundering processes for the treatment of fabrics to improve softness or hand normally are liquid fabric softener compositions which contain in a water vehicle a quartenary ammonium active component wherein all the hydrogen atoms of an ammonium radical are replaced by organic radicals. These cationic softener compounds have an afiinity for negatively-charged fibers and normally have at least one long chain alkyl radical of from 16 to 20 carbon atoms. It has been common in the formulation of softener compositions to include an optical brightening agent or fiuorescer to counteract the yellowing discoloration which often is associated with the use of cationic softening agents. Optical brighteners function by absorbing light in the invisible range (300-400 nm.) and remitting this as visible, blue-white light (400-500 nm.). This fluorescence masks the natural yellowing of textile fibers and results in a highly desirable blue-white glow on white goods and a fresher, cleaner appearance of colored goods. The use of softener formulations containing active brighteners often improves fabric whiteners to a level above that contributed by the detergent in the wash cycle. Addition of these brighteners to softening formulations intended for household use is common and such formula- '[lO'lS have been greatly preferred by the average housewr e.

While the prior art has known softener compositions capable of providing satisfactory softening and brightening properties to textile materials, none have been known to contribute to the cleaning process, i.e., soil removal. Prior the present invention, none of the known softener formulations have been known to be capable of attaining the improved whitening levels of the formulations employed in accordance with the present invention.

It is recognized that despite having been through a conventional laundering process including washing with a synthetic detergent formulation and subsequent treat ment with a conventional softener formulation during the normal rinse cycle or in a subsequent softener rinse, many fabrics still contain areas which are not completely free of soil. Much of the soil which remains in laundered fabrics is the result of redeposition of soil as the washing solution in a conventional washing machine containing suspended particulate and lipid soil is allowed to drain through the wash load prior to the rinsing cycle. The redeposited soil is loosely held by the laundered fabrics and except for that removed during the subsequent rinsing cycle remains with the fabric through and including the drying step of the home laundering process. The presence of such soil detracts from the overall whiteness and clean appearance of the laundered products.

In addition to lacking soil removal properties, the prior art softener compositions have for the most part been liquid formulations containing about 38% of cationic active. The liquid character of such softener compositions does not generally adversely affect their softening quality. However, it is often desirable from the standpoint of handling qualities to have a powdered or granulated softener formulation which will effectively soften textile materials. It is particularly advantageous with respect to packaging, storage and use to have a softening product which is solid in form. For example, the softening of textiles in home laundering situations is made more convenient by the use of a softening composition which may be added to the rinsing cycle in the form of a premeasured solid.

Other desirable aspects of a granular or solid softener composition are relative freedom from hydrolysis and the elmination of phase stability problems which are often encountered in the preparation of liquid formulations. For example, it is known that certain optional additives commonly employed in softening compositions have a tendency to become hydrolyzed as a result of which their effectiveness during storage is adversely affected as, for example, the bacteriocide 3,4,4-tri.chlorocarbanilide. This tendency to become hydrolyzed has renedered its applicability in aqueous compositions particularly disadvantageous. The utilization of such materials in softener formulations is rendered practicable in accordance with the present invention wherein the presence of substantial amounts of water is avoided by employing solid formulations. Phase stability problems which are encountred in liquid formulations frequently are the result of critical solubility levels and criticality in the relative proportions of ingredients employed. These critical aspects are such that exposure to certain climatic conditions has been known to result in a separation of discrete and marketable aspects of the formulation. The utilization of 3 granular compositions obviates the product stability problems previously encountered in liquid formulations.

It is an object of the present invention to provide a fabric softener composition of excellent softening properties in a solid or granular form.

A further object of this invention is to provide a fabric softener of improved cleaning and whitening properties. Other objects will become obvious from the description of the invention which hereinafter follows.

SUMMARY OF THE INVENTION These and other objects are achieved in accordance with the present invention which comprises the provision of a solid, granular fabric softener of improved cleaning and whitening properties which consists essentially of (a) From about 4 to about 50% of at least one cationic nitrogen-containing textile softener of the formula wherein each R is selected from the group consisting of 1) large organic groups containing from about 16 to about 24 carbon atom, said large organic groups containing from to about 3 either linkages, from 0 to about 2 amido linkages, from 0 to about 2 ester linkages, from 0 to about 2 hydroxy groups; and from 0 to l benzyl radical, and from 0 to about 1 imino group when the imino group connects two R groups to form an imidazoline ring, said organic groups containing an alkyl group of at least 16 carbon atoms without an interruption; (2) small organic groups containing from 1 to about 3 carbon atoms; and (3) hydroxy alkyl groups containing from 1 to about 3 carbon atoms; the R groups being selected so that (a) there are from 1 to 2 large, essentially straight chain, alkyl groups and (b) when there is only one large alkyl group in the compound it contains at least carbon atoms; and wherein X is selected from the group consisting of chloride, bromide, iodide, fluride, methyl sulfate and ethyl sulfate anions;

(b) From about to about 94% of at least one watersoluble organic polyphosphonate salt of the formula PoiM R1CRz POSMZ wherein R is hydrogen, lower alkyl (e.g., methyl, ethyl, propyl and butyl), aryl (e.g., phenyl and naphthyl), benzyl, halogen (e.g., chlorine, bromine, and fluorine), hydroxyl, amino, CH COOM, CH PO M or CH CH(PO M R is hydrogen, lower alkyl (e.g., methyl, ethyl, propyl, and butyl), benzyl, halogen (e.g., chlorine, bromine and fluorine), hydroxyl, CH COOM, -CH PO M or -CH CH PO M and M is a saltforming cation such as alkali metal (e.g., sodium and potassium), alkaline earth metal (e.g., calcium and magnesium), and ammonium or low molecular weight substituted ammonium (e.g., mono-, di-, and triethanolammonium), the pH of the composition being within the range from about 5.0 to about 11.0;

(c) From 0 to about 31% of at least one organic alkali metal-containing polyacetate sequestering agent, and

(d) From about 0.01 to about 4% of at least one cationic-compatible optical brightening agent, all percentages being by weight of the total composition.

The cationic nitrogen-containing softening agents useful in the exercise of the present invention are known fabric conditioning materials which impart softness and improved handling properties to the treated fabric. Representative of preferred cationic compounds which are preferred by reason of their excellent softening properties and ready availability are quaternary ammonium compounds which are characterized by the substitution of aliphatic hydrocarbyl groups for all of the hydrogens of an ammonium radical. These compounds may be represented by the aforesdescribed formula wherein each of the four R groups is an aliphatic hydrocarbyl group, i.e., it is comprised solely of carbon and hydrogen and the four R groups are selected so that (a) there are from 1 to 2 large essentially straight chain, alkyl groups of from about 16 to about 24 carbon atoms, and (b) from '2 to 3 alkyl groups of from 1 to about 3 carbon atoms and (c) when there is only one large aliphatic hydrocarbyl group in the compound it contains at least 20 carbon atoms. Especially preferred quaternary compounds which exhibit superior softening properties are those having two alkyl groups of from 18 to 24 carbons and two alkyl groups of from 1 to about 3 carbon atoms and those having one large alkyl group of from 22 to 24 carbon atoms and three alkyl groups of from 1 to about 3 carbon atoms. Examples of such compounds are the following cationic softening agents:

dimethyl dihexadecyl ammonium chloride dimethyl di(hydrogenated tallow alkyl) ammonium chloride dimethyl diheptadecyl ammonium chloride dimethyl dioctadecyl ammonium chloride dimethyl dinonadecyl ammonium chloride dimethyl diecosyl ammonium chloride dimethyl didocosyl ammonium chloride dimethyl ditetracosyl ammonium chloride eicosyl trimethyl ammonium chloride uncosyl trimethyl ammonium chloride docosyl trimethyl ammonium chloride tricosyl trimethyl ammonium chloride tetracosyl trimethyl ammonium chloride di(hydrogenated tallow alkyl) dimethyl ammonium methyl sulfate dihexadecyl diethyl ammonium chloride dihexadecyl dimethyl ammonium bromide Other suitable quaternary softeners are:

cicosyl-tri(2-hydroxyethyl) ammonium methyl sulfate uncosyl-tri(2-hydroxyethyl) ammonium methyl sulfate docosyl-tris(2-hydroxyethylammonium methyl sulfate tricosyl-tri(2-hydroxyethyl) ammonium methyl sulfate tetracosyl-tri(2-hydroxyethyl) ammonium methyl sulfate eicosyl tri( 2-hydroxyethyl) di(Z-benzyloctadecyl) dimethyl ammonium ethyl sulfate di (3 -oxa-eicosyl di 3'-hydroxypropyl) ammonium chloride di( 3,6,9-trioxa-pentacosyl) diethyl ammonium bromide di(2-hexadecyloxyethyl) dimethyl ammonium chloride di (2-stearoyloxyethyl) dimethyl ammonium chloride 2-stearoyloxyethyl triethyl ammonium chloride 2-hexadecyl- 1- 2-hydroxyethyl -imidazolinium chloride di(4-hydroxyoctadecyl)dimethyl ammonium ethyl sulfate 2,4,6-trihydroxyoctadecyl trimethyl ammonium chloride di( 3-stearamidopropyl dimethyl ammonium chloride Urea adducts of the aforementioned compounds prepared as disclosed in US. Pat. 3,256,180 of Walter E. .Weiss, issued June 14, 1966 also find applicability in the exercise of the present invention the disclosure of which is incorporated by reference.

The water-soluble polyphosphonate salts of the hereinbefore described formula:

P OQMZ l JR P o 3M as a result of their soil-removing tendencies, provide whitening levers heretofore unknown in softener formulations. In addition, they serve as carriers for the quaternary ammonium softeniug agents present in the claimed softener compositions of the present invention, imparting improved whitening and whiteness maintenance properties without adversely affecting the softening properties of cationic softening agents or the whitening properties of any optical brightening agent employed in accordance with the present invention.

Among the preferred polyphosphonates encompassed by the above formula are alkali, alkaline earth, ammonium and low molecular weight substituted ammonium salts of ethane-I-hydroxy-l,l-diphosphonic acid; methane-diphosphonic acid; methanehydroxydiphosphonic acid; ethane-1, 1,2-triphosphonic acid; propane-1,1,3,3-tetraphosphonic caid; ethane-Z-phenyl-l, l-diphosphonic acid; methanephenyldiphosphonic acid; ethane-l-amino-l,l-diphosphonic acid; methanedichlorodiphosphonic acid; nonane-5,5-diphosphonic acid; n-pentane-1,1-diphosphonic acid; methanedifiuorodiphosphonic acid; methanedibromodiphosphonic acid; propane-2,2-diphosphonic acid; ethane-Z-carboxy-l,l-diphosphonic acid; propane-l-hydroxy-1,1,3-triphosphonic acid; ethane-Z-hydroxy-1,1,2-triphosphonic acid, and propane-1,3-dipheny1-2,2-diphosphonic acid.

Mixtures of any of the foregoing phosphonic acid salts can be used in the compositions of this invention.

Ethane-l-hydroxy-l,l-diphosphonic acid, an especially preferred polyphosphonate, has the molecular formula CH C(OH) (PO H (According to nomenclature by radicals, the acid might also be named l-hydroxyethylidene diphosphonic acid.) The most readily crystallizable salt of this acid is obtained when three of the acid hydrogens are replaced by sodium. Hence, a preferred salt for the purpose of this invention is the trisodium hydrogen salt which has the structure:

This compound normally crystallizes as the hexahydrate which loses some water during air-drying to yield a mixture of the hexaand monohydrate averaging 3 to 4 molecules of water of hydration.

While any alkali, alkaline earth, ammonium or low molecular weight substituted ammonium salt of ethanel-hydroxy-l,l-diphosphonic acid can be used in the practice of this invention, the tetrasodium salt, the trisodum hydrogen salt, the disodium dihydrogen salt, the monosodium trihydrogen salt, the monocalcium salt and the mixtures thereof are preferred. The other sodium, potassium, ammonium, and mono-, di-, and triethanolammonmonium salts and mixtures thereof are also suitable. These compounds can be prepared by any suitable method, however, an especially preferred method is disclosed in copending application Ser. No. 553,648, filed May 31, 1966, by Oscar T. Quimby et al., and now US. Pat. 3,400,149.

Methanehydroxydiphosphonic acid and related compounds operable herein can be prepared, for example, by reaction of phosgene with an alkali metal dialkyl phosphite. A complete description of these compounds and the method for preparing same is found in copending patent application Ser. No. 517,073, filed Dec. 29, 1965, by Oscar T. Quimby, and now US. Pat. 3,422,137.

Methanedihosphonic acid and related compounds useful herein are described in detail in US. Pat. 3,213,030, granted Oct. 19, 1965. A preferred method of preparing such compounds is disclosed in copending application Ser. No. 218,862, filed Aug. 23, 1962, by Clarence H. Roy, and now US. Pat. 3,251,907.

Ethane-1,1,2-triphosphonic acid and related compounds which can be used in the formation of salt compositions of this invention, as well as a method for their preparation are fully described in copending patent application Ser. No. 602,161, filed Dec. 16, 1966, by Oscar T. Quimby.

Propane-1,1,3,3-tetraphosphonic acid and related compounds useful herein, and a method for preparing same are fully disclosed in copending application Ser. No. 507,662, filed Nov. 15, 1965, by Oscar T. Quimby, and now US. Pat. 3,400,176.

Pentane-2,2-diphosphonic acids and related compounds can be prepared in accordance with the method described by G. M. Kosolopoff in J. Amer. Chem. Soc., 75, 1500 (1953).

The alkali metal polyacetate sequestering agents which may be employed in the softener compositions of the present invention are normally employed to replace a part of the polyphosphonate salt which is used in the softener formulation and include, for example, ethylenediaminetetraacetates, N hydroxyethylethylenediaminetriacetates, diethylenetriaminepentaacetates and nitrilotriacetates. Examples of suitable compounds are the following:

Na ethylenediaminetetraacetate (EDTA) Na N-hydroxyethylethylenediaminetriacetate Na diethylenetriaminepentaactate Na 1,2-diaminocycloheXane-N,N'-tetraacetate Na N-nitriloethylenediaminetriacetate It will be appreciated, of course, that the above described sequestering agents are described by way of example only and that any of the organic sequestering agents known in the art may be employed to replace a portion of the polyphosphonate salt employed in the softener compositions of the present invention.

The optical 'brightener compounds employed in the present invention are essential compounds of the compositions of the present invention inasmuch as they contribute substantially to the high levels of brightening and whitenng preferred by the average housewife. Accordingly, optical brighteners of the hereinafter described types are employed to advantage in the compositions of the present invention.

Optical brighteners which may be employed in accordance with the present invention are fabric substantive compounds which are compatible with the hereinbefore described cationic nitrogen-containing softening agents. Suitable brightening agents are selected from the group consisting of (a) Bis-triazinyl-stilbenes of the formula I II soloM 2 wherein each X and Y is selected from the group consisting of and RO groups wherein R is alkyl of 1 to about 8 carbon atoms (e.g., methyl, ethyl, n-butyl, n-octyl); aryl of 6 to about 14 carbon atoms (e.g., phenyl, Z-naphthyl, 4-biphenylyl); hydroxy alkyl of from 1 to about 4 carbon atoms (e.g., 2-hydroxyethyl); and R is hydrogen; alkyl of 1 to about 8 carbon atoms; aryl of 6 to about 14 carbon atoms and hydroxyalkyl of 1 to about 4 carbon atoms or taken with R comprises a cycloaliphatic group (e.g., cyclohexyl); an aromatic group (e.g., benzo, naphtho) or an heterocyclic group (e.g., morpholino); and M is alkali metal (e.g., sodium, potassium); ammonium; lower molecular weight substituteed ammonium (e.g., mono-, diand triethanol-ammonium);

(b) Triazolyl-stilbenes of the formula:

wherein X is hydrogen; alkylamino of from 1 to about 8 carbon atoms (e.g., methylamino, ethylamino); arylamino of from 6 to about 10 carbon atoms (e.g., phenylamino) or R and R are each alkyl of 1 to about 8 carbon atoms (e.g., methyl, ethyl, propyl, n-butyl, n-octyl); aryl of 6 to about 12 carbon atoms (e.g., phenyl, biphenyl, naphthyl); or taken together comprise a cycloaliphatic (e.g., cyclohexyl) or aryl (benzo; naphtho; acenaphtho); M is as defined in Formula a;

(c) Mono-oxazoles of the formula:

wherein X is alkyl of 1 to about 18 carbon atoms (e.g.,

methyl, ethyl, n-propyl, n-undecyl, n-octadecyl); aryl of 6 to about 14 carbon atoms (phenyl, naphthyl); and each R and R is hydrogen; alkyl of 1 to about 8 carbon atoms or aryl of 6 to about 12 carbon atoms or when taken together R and R comprise a cycloalkyl or aryl group.

((1) Bis-oxazoles of the formula:

R, o o m -tn.

wherein R and R are defined as in Formula above;

(e) Bis-benzimidazoles of the formula:

wherein each X and Y is hydrogen or alkyl of 1 to about carbon atoms (e.g., methyl, ethyl, n-decyl) or hydroxyalkyl of from 1 to about 6 carbon atoms (e.g., 2-hydroxyethyl, 4-hydroxy-n-butyl, 6-hydroxy-n-hexyl);

(f) Coumarins of the formula:

wherein X is alkylamino of 1 to about 10 carbon atoms (e.g., ethylamino, dimethylamino); or arylamino of from 6 to about 14 carbon atoms (e.g., phenylamino); R and R are as defined in Formula 0 above;

(g) Pyrazines of the formula wherein each W, X, Y and Z is hydrogen; alkyl of from 1 to 8 carbon atoms (e.g., methyl, ethyl, propyl);

where R is an alkyl of from 1 to about 12 carbon atoms (e.g., ethylcarbamyl, butylcarbamyl); or alkylamino of from 1 to about 8 carbon atoms (e.g., dimethylamino);

(h) Pyrazolines of the formula wherein each X and Y is alkyl of 1 to about 8 carbon atoms (e.g., methyl, ethyl); aryl of 6 to about 14 carbon atoms (e.g., phenyl, naphthyl); sulfonamidophenyl (e.g., p-sulfonamidophenyl);

(i) Dibenzothiophenedioxides of the formula wherein each X is alkyl of l to about 18 carbon atoms (e.g., methyl, ethyl); aryl of 6 to about 14 carbon atoms (e.g., naphthyl); 4-alkoxybenzamido of the formula where R is an alkyl of from 1 to about 6 carbon atoms (e.g., 4-methoxybenzamido); and M is as defined in Formula a above.

Specific examples of brightener compounds useful in the present invention are cotton brighteners of the bistriazinyl-stilbene type such as 4,4'-bis- [4-anilino-6-di (hydroxyethyl) amino-symtriazin-2-ylamino] -2,2'-stilbenedisulf0nic acid,

disodium 4,4'bis 4-anilino-6-morpholino-sym-triazine-2- ylamino -2,2-stilbenedisulfonate,

disodium 4,4-bis- (4,6-dianilino-sym-triazin-2-ylamino 2,2-stilbenedisulfonate,

disodium 4,4-bis 4-anilino-6-ethylamino-sym-triazine 2-ylamino -2,2-stilbenedisulfonate and disodium 4,4'-bis (4-anilino-6-N-methylethanolaminosym-triazin-Z-ylamino -2,2-stilbenedisulfonate and disodium 4,4'-bis (4-anilino-6-diethanolamino-sym-triazin- 2-ylamino -2,2-stilbenesulfonate;

the triazolyl-stilbene type such as sodium-4-(2H-naphtho- [1,2-d] triazol-Z-yl -2-stilbenesulfonate;

Other brightener compounds which can be used are those which are especially suitable for brightening synthetic fibers. Examples of these brighteners include the monoazoles such as 2-n-octyl-naphth[1,2-d]oxazole; the bis-azoles such as 1,2-bis(S-methyl-Z-benzoxazolyl)ethylene; the bis-benzimidazoles such as N-hydroxyethyl-1,2- bis(benzimidazolyl)ethylene; the coumarin type such as 4-methyl-7-dimethylaminocoumarin and 3-phenyl-7-(diamino-sym-triazinylamino)coumarin; pyrazines such as 2,6 di(N,N-diethylamino)-5-di(ethylcarbamyl)pyrazine; the pyrazoline type such as l-p-sulfonamidophenyl-Elphenyl-2-pyrazoline; and the dibenzothiophenedioxide type such as 3,7-bis(p-methoxybenzoylamido)-dibenzothiophene-2,8-disulfonic acid-5,5-dioxide.

These and other brightener compounds which can be used in conjunction with the softening agents of the pres ent invention are disclosed in Stensby, Optical Brighteners in Fabric Softeners, Soap Chem. Specialties, 41, No. 5, -8 (May 1965), Netherlands Pat. 6,408,162 (Jan. 18, 1965), US. Pat. 2,950,253 (Aug. 23, 1960) and Kirk et al., Optical Brighteners, Encyclopedia Chem. Tech. 3, 737-50 (1965). It will be appreciated of course that the above recited examples of optical brighteners suitable for use in accordance with the present invention are listed by way of example only and any of the optical brighteners conventionally employed in the art can likewise be employed.

When the foregoing brightening agents are employed in the processes of the present invention, it has been found that good results are obtained when the brightener is present in the rinse solution in the amount of about 0.1 to about p.p.m. and most preferably from about 0.5 to about 3 p.p.m. Generally, these brightening agents are used in combination for best brightening results.

The solid softener formulations of the present invention may include minor amounts of optional materials which make the products of the present invention more effective or aesthetically attractive. For example, bacteriostatic and fungistatic agents such as hexachlorophene, 3,4',5 tribromosalicylanilide, 4,4-dichloro-3-(trifluoromethyl)carbanilide and 3,4,4-trichlorocarbanilide can be employed. Normally they are employed in amounts by weight of up to 2%. In addition perfumes and dyes may be employed in amounts up to 0.25% to render the products of the present invention aesthetically pleasing. While optional ingredients of the type hereinbefore described can be employed in the compositions of the present invention, certain materails known to be incompatible with components of the presently claimed compositions are to be avoided. For example, anionic detergents of the type conventionally known in the art are incompatible with quaternary softener compounds of the type employed according to the present invention and result in a loss of softening effect when employed in combination. Accordingly, anionic detergents are avoided in the compositions of the present invention.

As an embodiment of the present invention, the softener compositions described above are added in small amounts to the final rinsing bath of the laundering process. When so employed, they are added to the rinsing bath in an amount such that the rinse solution contains from about 25 to about 100 p.p.m. of cationic softener, from about 100 to about 400 p.p.m. of polyphosphonic acid salt, from zero to about 200 p.p.m. of alkali metal polyacetate sequestrant and from about 0.1 to about 5 p.p.m. of optical brightener all parts being by weight. For best softening and cleaning effect, it is preferred that the rinse solution contain about 40 to about 70 p.p.m. of softener and about 150 to about 300 p.p.m. of polyphosphonic acid salt.

The granular softener formulations of the present invention, being in dry form, can be employed in a particulate, flowing, granular form, the required amount of softener formulation being measured and added to the final rinsing bath of the laundering process. Alternatively, the softener formulations of the present invention can be compressed into tablets employing any of the conventional tabletting methods known in the art.

In another embodiment of the present invention, the softening compositions can be employed in the finishing of textiles in mill operations according to conventional padding bath procedures. The softening compositions of the present invention are solubilized in water so as to yield a solution of about 0.1 to 2.0% by Weight of softening agent. The fabrics to be treated are dipped or immersed in the aqueous solution, passed through a conventional roll mill and dried on a tenter frame or loop dryer.

The following examples illustrate the preparation of softener compositions of the present invention and are intended as being illustrative rather than limitative of the present invention.

EXAMPLE I Into a 400 ml. flask were added 46.2 grams of eicosyl trimethylammonium chloride at about room temperature (25 C.) and atmospheric conditions. To the flask were added, stirring by hand with the aid of a spatula, 8.1 grams of a solution consisting of approximately disodium 4,4'-bis(4-anilino 6 diethanolamino-symtriazin 2 ylamino) 2,2 stilbenesulfonate; 70% water and ethanol, all percentages being by weight. To the pasty mass resulting, 215 grams of the trisodium salt of ethane l hydroxy l,l diphosphonic acid were added and the mixture was stirred by hand until a substantially uniform mixture resulted.

The product, a substantially dry, granular mass, combined excellent softening, whitening and whiteness maintenance properties in the tests which hereinafter follow.

Substantially similar results can be obtained when the following brighteners are employed in lieu of disodium 4,4'-bis(4 anilino 6 diethanolamino-symtriazinQ-ylamino -2,2-stilbenesulionate:

4,4' bis-[4-anilino-6-di(hydroxyethyl)amino-sym-triazin- 2-ylamino]-2,Z-stilbenesulfonicacid;

disodium 4,4-bis(4-anilino-6-morpholino'sym-triazin- 2-ylamino -2,2-stilbenedisulfonate;

disodium 4,4-bis-(4,6-dianilino-sym-triazin-2- ylamino -2,2-stilbenedisulfonate;

disodium 4,4'-bis 4-anilino-6-ethylamino-sym-triazin-Z- ylamino)-2,2-stilbenedisulfonate and disodium 4,4-bis( 4-anilino-6-N-1nethylethanolaminosym-triazin-Z-ylamino)-2,2-stilbenedisulfonate;

sodium-4(2H-naphtho 1,2-d] triaZol-2-yl -2- stilbenesulfonate;

1,2-bis 5-methyl-2-benzoxazolyl ethylene;

N-hydroxyethyl-1,2-bis(benzimidazolyl)ethylene;

4-methyl-7-dimethylaminocoumarin and 3-phenyl-7-(diamino-sym-triazinylamino)coumarin;

2,6-di(N,N-diethylamino)-3,5-di(ethylcarbamyl)- pyrazine;

l-p-sulfonamidophenyl-3 -phenyl 2-pyrazoline;

3,7-bis(p-methoxybenzoylamido)-dibenzothiophene- 2,8-disulfonic acid-5,5-dioxide.

EXAMPLE II Into a household blender (Waring) were added 57.8 g. of the trisodium salt of ethane l hydroxy-l,l-diphosphonic acid and 10 grams of eicosyl trimethylammonium chloride. The mixture was blended until a substantially homogeneous mass had resulted and 3 grams of a solution of brightening agent in water and ethanol, described in Example I, were added to the mixture by spraying with the aid of an atomizer.

The formulation, a granular mass, provides excellent softening, whitening and brightening properties to laundered fabrics.

EXAMPLE III To a 400 ml. flask were added 115.6 grams of prescreened trisodium salt of ethane-l-hydroxy-l,l-diphosphonic acid. Screening was through a number 30 screen (Tyler standard). To the polyphosphonate salt were added 20 grams of eicosyl trimethylammonium chloride and 6 grams of a solution of optical brightener described in Example 1. Upon mixing with the aid of a spatula, a dry, almost free-flowing powder resulted. The formulation when added to the rinse cycle of the laundering process improves the appearance of white and colored laundered fabrics.

In the above examples (I to III), substantially similar results can be obtained when the following softening agents are substituted for eicosyl trirnethylammonium chloride.

dimethyl dihexadecyl ammonium chloride dimethyl di(hydrogenated tallow alkyl) ammonium chloride dimethyl diheptadecyl ammonium chloride dimethyl dioctadecyl ammonium chloride dimethyldinonadecyl ammonium chloride dimethyl dieicosyl ammonium chloride dimethyl didocosyl ammonium chloride dimethyl ditetracosyl ammonium chloride uncosyl trimethyl ammonium chloride docosyl trimethyl ammonium chloride tricosyl trimethyl ammonium chloride tetracosyl trimethyl ammonium chloride EXAMPLE IV Into a 400 ml. flask is added 50 grams of di(hydrogenated tallow alkyl) dimethyl ammonium chloride at approximately room temperature C.). To the flask is added, with stirring by hand with the aid of a spatula, 8 grams of a brightener premix containing approximately 10% disodium 4,4-bis(4-anilino-6-diethanolarnino-symtriazin-Z-ylamino) 2,2 stilbenesulfonate; 70% water and 20% ethanol. To the pasty mass resulting, 170 grams of the trisodium salt, of ethane 1 hydroxy-l,l-diphosphonic acid and 55 grams of Na N-nitriloethylenediaminetriacetate are added with stirring until a substantially uniform mixture results.

The product, a substantially dry, granular mass improves the softening, whitening, brightening and whiteness maintainance of most laundered fabrics.

Substantially similar results are obtained when the following compounds are employed in lieu of the trisodium salt of ethane-l-hydroxy-l,l-diphosphonic acid: alkali, alkaline earth, ammonium salts of methane-diphosphonic acid, propane-l,l,3,3-tetraphosphonic acid and ethane-2- hydroxy-l,1,2-triphosphonic acid.

EVALUATION OF SOFTENE R COMPOSITIONS A wash-wear test described below, using standardized detergent compositions was conducted to determine the relative effectiveness of granular softener formulations containing a polyphosphonate salt as compared with conventional liquid formulations containing a cationic nitrogen-containing softening agent and brightener. The liquid formulation did not contain a polyphosphonate salt.

The wash-wear test was conducted in the following manner. White dress shirts, cotton T-shirts and other fabrics were distributed among various individuals. Each dress shirt and T-shirt was worn for one normal working day under uniform conditions and the other articles were used for their intended purposes. The soiled clothes and fabrics along with clean wash-cloth size swatches of terry cloth and muslin were then washed in an automatic agitating-type Washer having a water volume of 16 gallons for a 10 minute period with detergent solutions at 130 F. The wash Water had an average hardness of 9 grains per gallon. After washing, the clothes and fabrics were subjected to a 2-minute softener-containing rinse cycle at 100 F. In some instances the temperature during rinse was 80' F. The pH of the rinse water was 7.5.

The softener formulations employed during the rinse 70 cycle for comparison purposes constituted (1) a liquid formulation containing 5.25% of a cationic nitrogencontaining softening agent, and 0.22% of brightener and (2) the granular formulation of Example I. The ingredients of the softener formulations employed in the tests and their concentrations in rinse water are shown as follows:

Direct comparison were made by separate panels of housewives and experts between pairs of shirts and fabrics worn and soiled by the same individual. The dress shirts, T-shirts and other fabrics were graded on the degree of softness, whiteness and whiteness maintenance. For purposes of this invention, the term whiteness is intended as referring to the overall whiteness impression of areas which are only slightly or moderately soiled as, for example, the expansion portions of white dress shirts as opposed to the more heavily-soiled collars and cuffs. Improved whitening or whiteness impression may be the result of soil removal, i.e., a cleaning phenomenon, the result of the use of an an optical brightener or both. Whiteness maintenance or whitening retention refers to the capacity of a laundering composition to prevent redeposition of soil which is removed from a Washed fabric. Whiteness maitenance may be determined by comparing the whiteness of clean washcloth size swatches of cotton terry cloth and muslin both before and after washing along with soil fabrics.

The gradings of the test panelists showed the granuler softener formulation of the present invention to have excellent softening, whitening and whiteness maintenance effects. Whereas the softeness or hand imparted by the granular formulation was at least equal to that imparted by the liquid formulation which contained no polyphosphonate, the composition of the present invention containing added polyphosphonate resulted in both improved whiteness levels and superior whiteness maintenance as indicated by higher panelist grades.

The improved whitening and whiteness maintenance resulting from the use of a low concentration of polyphosphonate salt during the rinsing cycle was unexpected, particularly in view of the fact that the pH of the rinse water was in the range of 7 to 8 which is below the pH range of 9 to 12. in which range, salts of polyphosphonates exhibit their best sequestering and building properties.

The finding of improved whiteness without loss of softening was also unexpected. For example, certain inorganic sequestering agents such as sodium tripolyphoshate, tetrapotassium pyrophosphate and trisodiummetaphosphate are not compatible with cationic softeners and when used in combination destroyed the softening function of the softener component. The use of a combination of cationic softener and inroganic phosphate sequestrant results in no perceptible softening when employed during the conventional rinse cycle. Similarly, incompatibility is found between cationic softeners and certain antiredeposition agents. A common soil anti-redeposition agent, carboxymethyl cellulose, when present in the final rinse causes an appreciable drop in the softening effect of the cationic softener.

While applicant does not wish to be bound by any particular theory as to the precise nature of the unexpected levels of softening, whitening and whiteness maintenance found in the use of a low concentration of polyphosphonate during the rinse cycle, it is believed that a complex interrelation of sequestration and anti-redeposition phenomena is involved.

What is claimed is:

1. The method of imparting improved cleaning, brightening and softening properties to laundered textiles which comprises rinsing said textiles in an aqueous rinsing bath consisting essentially of water and 13 (a) from about 25 p.p.m. to about 100 ppm. of a cationic nitrogen-containing textile softener of the wherein R R R and R are each selected from the group consisting of (1) alkyl groups of from about 16 to about 24 carbon atoms, said alkyl groups containing from to about 3 ether linkages, from 0 to about 2 amido linkages, from 0 to about 2 ester linkages, from 0 to about 2 hydroxy groups, from ID to 1 benzyl radical, and from 0 to about 1 imino group when the imino group connects two R groups to form an imidazoline ring, said alkyl groups having at least 16 carbon atoms without an interruption; (2) alkyl groups containing from about 1 to 3 carbon atoms, and (3) hydroxy alkyl groups containing from 1 to about 3 carbon atoms; said R groups being 1 selected so that (a) there are one or two essentially straight chain, alkyl groups of from about 1 6 to about 24 carbon atoms and (b) when there is only one of said essentially straight chain alkyl groups it has at least 20 carbon atoms; and wherein X is selected from the group consisting of chloride, bromide, iodide, fluoride, ethyl sulfate and ethyl sulfate anions; (b) from about 100 ppm. to about 400 p.p.rn. of a water-soluble organic polyphosphonate salt of the formula POsM R;--(3R POsMg wherein R is hydrogen, lower alkyl, phenyl, naphnthyl, benzyl, halogen, hydroxyl, amino,

R is hydrogen, lower alkyl, benzyl, halogen, hydroxyl, --CH COOM, -CH PO M or and M is a salt-forming cation selected from alkali metal, alkaline earth metal, ammonium, monoethanol ammonium, diethanolammonium, and triethanolarnmonium, the pH of the composition being within the range from about 5. 0 to about 11.0;

(c) from *0 p.p.m. to about 200 p.p.rn. of an organic alkali metal-containing polyacetate sequestering agent selected from the group consisting of ethylenediarninetetraacetates, N hydroxyethylethylenediaminetriacetates, diethylenetriaminepentaacetates, and nitrolotriacetates, and

(d) from about 0.1 ppm. to about p.p.rn. of a cationic-compatible optical brightening agent.

2. The method of claim 1 wherein the polyphosphonate salt is a salt of ethane-1-hydroxy-1,l diphosphonic acid.

3. The method of claim 1 wherein the optical brightener is selected from the group consisting of (a) bis-triazinyl-stilbenes of the formula wherein each X and Y is selected from the group consisting of NH- R/ and :RO- groups wherein R is alkyl of 1 to about 1 8 carbon atoms; aryl of 6 to about 14 carbon atoms; hydroxyalkyl of from 1 to about 4 carbon atoms; and R is hydrogen; alkyl of 1 to about 8 carbon atoms; aryl of 6 to about 14 carbon atoms and hydroxyalkyl of 1 to about 4 carbon atoms or taken with R comprises a cycloaliphatic group; an aromatic group or an heterocyclic group; and M is alkali metal; ammonium; lower molecular weight substituted ammonium; (b) triazolyl-stilbenes of the formula:

wherein X is hydrogen; alkylarnino of from 1 to about 8 carbon atoms; arylamino of from 6 to about 10 carbon atoms or 1 wherein X is alkyl of 1 to about 18 carbon atoms; aryl of 6 to about 14 carbon atoms; and each R and R is hydrogen; alkyl of 1 to about 8 carbon atoms or aryl of 6 to about 12 carbon atoms or when taken together R and -R comprise a cycloalkyl group or an aryl group;

(d) bis-oxazoles of the formula:

: s th wherein R and R are defined :as in Formula 0 above; (e) bis-benzimidazoles of the formula:

wherein each X and Y is hydrogen or alkyl of 1 to about 10 carbon atoms or hydroxyalkyl or from 1 to about 6 carbon atoms;

(f) coumarins of the formula:

wherein X is alkylamino of 1 to about 10 carbon atoms; or arylamino of from about 6 to about 14 car- 15 bon atoms; R and -R are as defined in Formula c above; (g) pyrazines of the formula:

wherein each W, X, Y and Z is hydrogen; alkyl of from 1 to 8 carbon atoms; 'R NHC(O)- where R is an alkyl of 1 to about 12 carbon atoms; or alkylamino of from 1 to about 8 carbon atoms;

(h) pyrazolines of the formula:

wherein each X and Y is alkyl of 1 to about 8 carbon atoms; aryl of '6 to about 14 carbon atoms; and sulfonamidophenyl;

(i) dibenzothiophenedioxide of the formula MO3S- SO3M X- \S -X 0 wherein each X is alkyl of 1 to about 18 carbon atoms; aryl of 6 to about 14 carbon atoms; 4-alkoxybenzamido of the formula:

RO JZW 1 6 bri-ghtener of disodium 4,4'-bis(4-anilino-6-diethanolamino-sym-triazin-2-ylamino) 2,2-stilbenesulfonate.

5. The method of claim 1 wherein R R R and R of the cationic softening agents are each alkyl groups and are selected so that (a) there are from 1 to 2 essentially straight chain, alkyl groups of from 16 to about 24 carbon atoms (b) from 2 to 3 alkyl groups of 1 to about 3 carbon atoms and (c) When there is only one of said essentially straight chain alkyl groups it contains at least 20 carbon atoms.

6. The method of claim 5 wherein the polyphosphonate salt is a salt of ethane-l-hydroxy-l,1-diphosphonic acid.

7. The method of claim 6 wherein the organic alkali metal-containing sequestering agent is a nitrolotriacetate.

References Cited UNITED STATES PATENTS 3,159,581 12/1964 Diehl 252152 3,213,030 10/1965 Diehl 252-152 3,351,483 11/1-967 Miner et a1. 2528.8X 3,356,526 12/1967 Waldman et al. 117139.5X 3,360,470 12/1967 Wixon 2528.75X 3,394,083 7/1968 Shen 252152X 3,400,148 9/1968 Quimby 2528.'6X

FOREIGN PATENTS 713,521 7/1965 Canada 2528.8 3,207 2/ 1967 Canada.

OTHER REFERENCES Stensby, Optical Brighteners in Fabric Softeners, article in Soap and Chemical Specialties, May 1965, pp. 88.

HERBET B. GUYN'N, Primary Examiner U.S. Cl. X.=R.

gggg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,591,405 Dated Jul 6, 1971 Inventor(s) Charles Bruce McCarty It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

r- Column 2, line 71, after "discrete" insert phases which .1

separation adversely affects the aesthetic Column 3, line 27, "either" should be ether Column 3, line 41, "fluride" should be fluoride Column 5, line 14, "caid" should be acid Column 6, line 37, "compounds should be components Column 12, line 21, "expansion" should be expansive Column 12, line 54, "destroyed" should be destroy Column 13, line 27, "ethyl sulfate" should be methyl sulfate Column 16, line 1, "of" should be is Signed and sealed this 22nd day of February 1972.

( Attest:

EDWARD M.FLETCHEH, JR. ROBERT GOTTSCHALK Attesting Officer Co missioner of Patents 

